Detergency builder system

ABSTRACT

A highly effective detergency builder system comprises the combination of a major proportion of an ether polycarboxylate and minor proportions of an iron and manganese chelating agent and a polymeric polycarboxylate dispersing agent.

This application is a continuation-in-part of co-pending U.S. patentapplication Ser. No. 702,521, filed Feb. 19, 1985, now abandoned.

TECHNICAL FIELD

The present invention relates to detergency builder systems useful indetergent compositions.

BACKGROUND ART

The term detergency builder can be applied to any component of adetergent composition which increases the detergent power of a surfaceactive agent, hereinafter surfactant. Generally recognized functions ofdetergency builders include removal of alkaline earth and otherundesirable metal ions from washing solutions by sequestration orprecipitation, providing alkalinity and buffer capacity, prevention offloculation, maintenance of ionic strength, protection of anionicsurfactants from precipitation and extraction of metals from soils as anaid to their removal. Polyphosphates such as tripolyphosphates andpyrophosphates are widely used as ingredients in detergent compositionsand are highly effective detergency builders. However, the effect ofphosphorus on eutrophication of lakes and streams has been questionedand the use of phosphates in detergent compositions has been subject togovernment regulation or prohibition.

These circumstances have developed a need for highly effective andefficient phosphorus-free detergency builders. Many materials andcombinations of materials have been used or proposed as detergencybuilders. Carbonates and silicates are widely used in granular detergentcompositions, but by themselves are deficient as detergency builders ina number of respects. Aluminosilicates such as described in U.S. Pat.No. 4,274,975, issued June 23, 1981, to Corkill et al., have also beenused to replace polyphosphates. Aluminosilicates, however, haverelatively low calcium and magnesium binding constants and can presentsolubility problems, particularly in combination with silicates.

Ether polycarboxylates having one or more units of the structure##STR1## wherein M is hydrogen, an alkali metal, ammonium or substitutedammonium cation, have been proposed as detergency builder substitutesfor polyphosphates. The ether polycarboxylates need not containphosphorus or nitrogen (also subject to environmental concerns when usedin large amounts) and can be more rapidly biodegradable than polymericpolycarboxylates. Ether polycarboxylates are one of the essentialcomponents of the present invention.

U.S. Pat. No. 3,293,176, issued Dec. 20, 1966, to White, discloses etherchelating compounds having carboxylic acid, phosphoric acid or sulfonicacids groups.

U.S. Pat. No. 3,692,685, issued Sept. 19, 1972 to Lamberti et al.,discloses detergent compositions containing an ether polycarboxylatehaving the formula: ##STR2## wherein R is H or CH₂ COONa

U.S. Pat. No. 4,228,300, issued Oct. 14, 1980, to Lannert, disclosesether polycarboxylate sequestering agents and detergency builders havingthe formula ##STR3## wherein M is alkali metal or ammonium, R₁ and R₂are hydrogen, methyl or ethyl and R₃ is hydrogen, methyl, ethyl or COOM.

U.S. Pat. Nos. 3,923,679, issued Dec. 2, 1975, and 3,835,163, issuedSept. 10, 1974, both to Rapko, disclose 5-membered ring ethercarboxylates. U.S. Pat. Nos. 4,158,635, issued June 19, 1979; 4,120,874,issued Oct. 17, 1978, and 4,102,903, issued July 25, 1978, all toCrutchfield et al. disclose 6-membered ring ether carboxylates.

U.S. Pat. No. 3,776,850, issued Dec. 4, 1973, to Pearson et al.,discloses polymers to be used as detergent builders having the formula:##STR4## wherein R is hydrogen or other specified radicals and n is from2 to about 40, preferably from 2 to about 6.

U.S. Pat. No. 4,146,495, issued Mar. 27, 1979, to Crutchfield et al.,incorporated herein by reference, discloses a method of preparingpolyacetal carboxylate detergency builders containing the structure##STR5## wherein M is alkali metal, ammonium, tetralkylammonium oralkanolamine and n averages at least 4.

Many, but not necessarily all, ether polycarboxylates, are deficient incalcium binding power relative to inorganic polyphosphates. This isrecognized and modifications to detergent compositions have beensuggested to overcome this and other deficiencies. The suggestionsinclude an increase in surfactant level and combination with inorganicalkaline materials such as sodium silicate and sodium carbonate.

It has now been found that ether polycarboxylate materials with acalcium binding constant (expressed as log K_(Ca)) above a specifiedminimum value can be successfully incorporated in detergent compositionsas part of a builder system comprising three types of organic detergencybuilders. The resultant detergent compositions provide, in a no or lowphosphate composition, fabric cleaning in a household laundry contextessentially equivalent to that provided by compositions containing fromabout 25% to about 50% by weight of an alkali metal polyphosphate suchas sodium tripolyphosphate. The additional builders are designated ironand manganese chelating agents and polymeric polycarboxylate dispersingagents herein.

SUMMARY OF THE INVENTION

The detergent compositions of the invention contain as essentialingredients:

(a) from about 2% to about 30% by weight of a surfactant selected fromthe group consisting of anionic, nonionic, zwitterionic, ampholytic andcationic surfactants and mixtures thereof,

(b) from about 4% to about 50% by weight of an ether polycarboxylatecompound or mixtures thereof having one or more units of the structure##STR6## wherein M is hydrogen, an alkali metal, ammonium or substitutedammonium and said compound has a log K_(Ca) (35° C., 0.1M ionicstrength, pH 9.5) of at least about 3.6,

(c) from about 0.1% to about 10% by weight of an iron and manganesechelating agent as hereinafter defined,

(d) from about 0.5% to about 10% by weight of one or more polymericpolycarboxylic acid dispersing agents, copolymers thereof and saltsthereof containing at least 60% by weight of segments having thestructure: ##STR7## wherein X, Y and Z are each selected from the groupconsisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy andhydroxymethyl; and n is from about 30 to about 400,

(e) from 0% to about 75%, and in a granular or tablet form composition,preferably from about 15% to about 60%, by weight of an inorganicdetergency builder selected from the group consisting of alkali metalphosphates, sodium carbonate, sodium silicate, sodium aluminosilicateand mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

The detergent compositions of the invention can be prepared in solid orliquid physical form.

The detergent compositions of the invention are particularly suitablefor laundry use, but are also suitable for the cleaning of hard surfacesand for dishwashing.

In a laundry method aspect of the invention, typical laundry wash watersolutions comprise from about 0.1% to about 1% by weight of thedetergent compositions of the invention.

THE SURFACTANT

The compositions of the invention contain from about 2% to about 30% byweight of a surfactant or mixtures thereof.

Various types of surfactants can be used in the compositions of theinvention. Useful surfactants include anionic, nonionic, ampholytic,zwitterionic and cationic surfactants or mixtures of such materials.Detergent compositions for laundry use typically contain from about 5%to about 30% anionic surfactants or mixtures of anionic and nonionicsurfactants. Detergent compositions for use in automatic diswashingmachines typically contain from about 2% to about 6% by weight of arelatively low sudsing nonionic surfactant or mixtures thereof and,optionally, suds control agents. Particularly suitable low sudsingnonionic surfactants are the alkylation products of compounds containingat least one reactive hydrogen wherein, preferably, at least about 20%by weight of the alkylene oxide by weight is propylene oxide. Examplesare products of the BASF-Wyandotte Corporation designated Pluronic®,Tetronic®, Pluradot® and block polymeric variations in whichpropoxylation follows ethoxylation. Preferred suds control agentsinclude mono-and disteryl acid phosphates.

(A) Anionic soap and non-soap surfactants

This class of surfactants includes ordinary alkali metalmonocarboxylates (soaps) such as the sodium, potassium, ammonium andalkylolammonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms and preferably from about 12 to about 18 carbonatoms. Suitable fatty acids can be obtained from natural sources suchas, for instance, from plant or animal esters (e.g., palm oil, coconutoil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils,grease, lard, and mixtures thereof). The fatty acids also can besynthetically prepared (e.g., by the oxidation of petroleum, or byhydrogenation of carbon monoxide by the Fischer-Tropsch process). Resinacids are suitable such as rosin and those resin acids in tall oil.Naphthenic acids are also suitable. Sodium and potassium soaps can bemade by direct saponification of the fats and oils or by theneutralization of the free fatty acids which are prepared in a separatemanufacturing process. Particularly useful are the sodium and potassiumsalts of the mixtures of fatty acids, derived from coconut oil andtallow, i.e., sodium or potassium tallow and coconut soap.

Soaps and fatty acids also act as detergency builders in detergentcompositions because they remove multivalent ions by precipitation.

Anionic surfactants also includes water-soluble salts, particularly thealkali metal and ethanolamine salts of organic sulfuric reactionproducts having in their molecular structure an alkyl radical containingfrom about 8 to about 22 carbon atoms and a sulfonic acid or sulfuricacid ester radical. (Included in the term alkyl is the alkyl portion ofalkylaryl radicals.) Examples of this group of non-soap anionicsurfactants are the alkyl sulfates, especially those obtained bysulfating the higher alcohols (C₈ -C₁₈ carbon atoms); alkyl benzenesulfonates, in which the alkyl group contains from about 9 to about 15carbon atoms, in straight chain or branched chain configuration, sodiumalkyl glyceryl ether sulfonates; fatty acid monoglyceride sulfonates andsulfates; sulfuric acid esters of the reaction product of one mole of aC₁₂₋₁₈ alcohol and about 1 to 6 moles of ethylene oxide; salts of alkylphenol ethylene oxide ether sulfate with about 1 to about 10 units ofethylene oxide per molecule and in which the alkyl radicals containabout 8 to about 12 carbon atoms.

Additional examples of non-soap anionic surfactants are the reactionproduct of fatty acids esterified with isothionic acid and neutralizedwith sodium hydroxide where, for example, the fatty acids are derivedfrom coconut oil; sodium or potassium salts of fatty acid amide ofmethyl lauride in which the fatty acids, for example are derived fromcoconut oil.

Still other anionic surfactants include the class designated assuccinamates. This class includes such surface active agents as disodiumN-octadecylsulfosuccinamate; tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinamate; the diamyl ester ofsodium sulfosuccinic acid and the dihexyl ester of sodium sulfosuccinicacid; dioctyl ester of sodium sulfosuccinic acid.

Anionic phosphate surfactants are also useful in the present invention.These are surface active materials having substantial detergentcapability in which the anionic solubilizing group connectinghydrophobic moieties is an oxy acid of phosphorus. The more commonsolubilizing groups, of course are --SO₄ H, --SO₃ H, and --CO₂ H. Alkylphosphate esters such as (R--O)₂ PO₂ H and ROPO₃ H₂ in which Rrepresents an alkyl chain containing from about 8 to about 20 carbonatoms are useful.

These esters can be modified by including in the molecule from one toabout 40 alkylene oxide units, e.g., ethylene oxide units.

Particularly useful anionic surfactants useful herein are alkyl ethersulfates. The alkyl ether sulfates are condensation products of ethyleneoxide and monohydric alcohols having about 10 to about 20 carbon atoms.Preferably, R has 14 to 18 carbon atoms. The alcohols can be derivedfrom fats, e.g., coconut oil or tallow, or can be synthetic. Suchalcohols are reacted with 1 to 30, and especially 3 to 6, molarproportions of ethylene oxide and the resulting mixture of molecularspecies, having, for example, an average of 3 to 6 moles of ethyleneoxide per mole of alcohol, is sulfated and neutralized.

Other suitable anionic surfactants are olefin and paraffin sulfonateshaving from about 12 to about 24 carbon atoms.

(B) Nonionic surfactants

Alkoxylated nonionic surfactants may be broadly defined as compoundsproduced by the condensation of alkylene oxide groups (hydrophilic innature) with an organic hydrophobic compound, which may be aliphatic oralkyl aromatic in nature. The length of the hydrophilic orpolyoxyalkylene radical which is condensed with any particularhydrophobic group can be readily adjusted to yield a water-solublecompound having the desired degree of balance between hydrophilic andhydrophobic elements.

Alkoxylated nonionic surfactants include:

(1) The condensation product of aliphatic alcohols having from 8 to 22carbon atoms, in either straight chain or branched chain configuration,with from about 5 to about 20 moles of ethylene oxide per mole ofalcohol.

(2) The polyethylene oxide condensates of alkyl phenols, e.g., thecondensation products of alkyl phenols having an alkyl group containingfrom about 6 to 12 carbon atoms in either a straight chain or branchedchain configuration, with ethylene oxide, the said ethylene oxide beingpresent in amounts equal to 5 to 25 moles of ethylene oxide per mole ofalkyl phenol. The alkyl substituent in such compounds may be derivedfrom polymerized propylene, diisobutylene, octene, or nonene, forexample.

(3) Materials derived from the condensation of ethylene oxide with aproduct resulting from the reaction of propylene oxide and a compoundwith reactive hydrogen such as glycols and amines such as, for example,compounds containing from about 40% to about 80% polyoxyethylene byweight resulting from the reaction of ethylene oxide with a hydrophobicbase constituted of the reaction product of ethylene diamine andpropylene oxide.

Non-polar nonionic surfactants include the amine oxides andcorresponding phosphine oxides. Useful amine oxide surfactants includethose having the formula R¹ R² R³ N→O wherein R¹ is an alkyl groupcontaining from about 10 to about 28 carbon atoms, from 0 to about 2hydroxy groups and from 0 to about 5 ether linkages, there being atleast one moiety of R¹ which is an alkyl group containing from about 10to about 18 carbon atoms and no ether linkages, and each R² and R³ areselected from the group consisting of alkyl radicals and hydroxyalkylradicals containing from 1 to about 3 carbon atoms;

Specific examples of amine oxide surfactants include:dimethyldodecylamine oxide, dimethyltetradecylamine oxide,ethylmethyltetradecylamine oxide, cetyldimethylamine oxide,diethyltetradecylamine oxide, dipropyldodecylamine oxide,bis-(2-hydroxyethyl)dodecylamine oxide,bis-(2-hydroxypropyl)methyltetradecylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, and the corresponding decyl,hexadecyl and octadecyl homologs of the above compounds.

(C) Zwitterionic Surfactants

Zwitterionic surfactants include derivatives of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds in which the aliphaticmoiety can be straight or branched chain and wherein one of thealiphatic substituents contains from about 8 to 24 carbon atoms and onecontains an anionic water-solubilizing group. Particularly preferredzwitterionic materials are the ethoxylated ammonium sulfonates andsulfates disclosed in U.S. Pat. Nos. 3,925,262, Laughlin et al, issuedDec. 9, 1975 and 3,929,678, Laughlin et al, issued Dec. 30, 1975, saidpatents being incorporated herein by reference.

(D) Ampholytic Surfactants

Ampholytic surfactants include derivatives of aliphatic heterocyclicsecondary and ternary amines in which the aliphatic moiety can bestraight chain or branched and wherein one of the aliphatic substituentscontains from about 8 to about 24 carbon atoms and at least onealiphatic substituent contains an anionic water-solubilizing group.

(E) Cationic Surfactants

Cationic surfactants comprise a wide variety of compounds characterizedby one or more organic hydrophobic groups in the cation and generally bya quaternary nitrogen associated with acid radical. Pentavalent nitrogenring compounds are also considered quaternary nitrogen compounds.Suitable anions are halides, methyl sulfate and hydroxide. Tertiaryamines can have characteristics similar to cationic surfactants atwashing solutions pH values less than about 8.5.

A more complete disclosure of cationic surfactants can be found in U.S.Pat. No. 4,228,044, issued Oct. 14, 1980, to Cambre, said patent beingincorporated herein by reference.

When cationic surfactants are used in combination with anionicsurfactants and certain detergency builders including polycarboxylates,compatibility must be considered. A type of cationic surfactantgenerally compatible with anionic surfactants and polycarboxylates is aC₈₋₁₈ alkyl tri C₁₋₃ alkyl ammonium chloride or methyl sulfate.

More complete disclosures of surfactants suitable for incorporation indetergent compositions of the invention are in U.S. Pat. Nos. 4,056,481,Tate (Nov. 1, 1977); 4,049,586, Collier (Sept. 20, 1977); 4,040,988,Vincent et al (Aug. 9, 1977); 4,035,257, Cherney (July 12, 1977);4,033,718, Holcolm et al (July 5, 1977); 4,019,999, Ohren et al (Apr.26, 1977); 4,019,998, Vincent et al (Apr. 26, 1977); and 3,985,669,Krummel et al (Oct. 12, 1976); all of said patents being incorporatedherein by reference.

THE DETERGENCY BUILDER SYSTEM A. Ether Polycarboxylate

The compositions of the invention contain from about 4% to about 50%,and in solid form detergent compositions, preferably from about 15% toabout 40%, of an ether polycarboxylate compound or mixtures thereofhaving one or more units of the general structure ##STR8## wherein M ishydrogen, an alkali metal, ammonium or substituted ammonium and saidcompound has a log K_(Ca) (35° C., 0.1M molar strength, pH 9.5) of atleast about 3.6, preferably at least about 4.2. Compounds with thisstructure provide calcium binding by formation of polydentatestructures. Ether carboxylates with log K_(Ca) values above about 5 orgreater are more nearly equivalent to polyphosphates for fabric cleaningwithout the additional organic detergency builder components of thepresent invention, but nevertheless all ether polycarboxylates tend tobe somewhat deficient when used as a direct replacement forpolyphosphates on a mole equivalent basis.

Ether polycarboxylates having the structure: ##STR9## wherein R₁ and R₂are each H, COOM or CH₂ COOM and M is H, alkali metal, ammonium orsubstituted ammonium constitute embodiments of the inventionparticularly benefited by the combination with iron and manganesechelating agents and polymeric polycarboxylate dispersing agents.

Specific ether polycarboxylates particularly benefited include2-oxa-1,1,3-propanetricarboxylates, 2-oxa-1,3,4-butanetricarboxylates,3-oxa-1,2,4,5-pentanetetracarboxylates and polyacetal carboxylateshaving the structure ##STR10## wherein M is hydrogen or a monovalentcation, n averages at least 4, preferably at least about 50, and R₁ andR₂ are groups to stabilize against rapid depolymerization in alkalinesolution such as disclosed in U.S. Pat. No. 4,144,226 issued Mar. 13,1979, to Crutchfield et al, incorporated herein by reference.

A method for the preparation of 2-oxa-1,1,3-propanetricarboxylic acid isdisclosed in U.S. Pat. No. 4,228,300, issued Oct. 14, 1980, to Lannert,incorporated herein by reference.

A method for the preparation of 2-oxa-1,3,4-butanetricarboxylic acid isdisclosed in U.S. Pat. No. 3,692,685, issued Sept. 19, 1972, to Lambertiet al, incorporated herein by reference.

A method for the preparation of 3-oxa-1,2,4,5-pentanetetracarboxylicacid is disclosed in U.S. Pat. No. 3,128,287 issued Apr. 7, 1964, toBerg, incorporated herein by reference.

Crutchfield, M. M., J. Am. Oil Chemists' Soc. 55:58 (1978), incorporatedherein by reference, lists log K_(Ca) values of a large number of etherpolycarboxylates suitable for use in detergent compositions of thepresent invention.

Also suitable in the compositions of the invention are the3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Ser. No. 672,302 filed Nov. 16, 1984, and incorporatedherein by reference.

Suitable ether polycarboxylates include cyclic compounds, particularlyalicyclic compounds, provided they have the essential substructuredescribed hereinbefore. U.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635;4,120,874 and 4,102,903 discussed hereinbefore, incorporated herein byreference, disclose such cyclic ether polycarboxylates.

CALCIUM BINDING CONSTANT DETERMINATION

A computer system (Hewlett-Packard) with digital voltmeters was used tocollect and analyze data from an Orion calcium selective electrode and alinear syringe buret (Sage Instruments syringe pump plus a linearpotentiometer). An Analog Devices 40J non-inverting operationalamplifier electrometer amplified the calcium electrode voltage andprovided Nernstian behavior of the electrode into the 10⁻⁷ M range.Volumetric accuracy was better than +/-0.5%.

Three hundred data pairs of [Ca total] vs 10.sup.(E/S), which is alinear measure of [Ca free], were collected and corrected for dilutionduring each titration. S is the Nernst equation slope, ca. 29 mv/decade,and E is the calcium electrode voltage. Calcium ion was titrated intobuffer solution. Here, L represents the sequestering ligand. Aligand-free standard titration calibrated the electrode response. Asecond titration, containing a fixed concentration of total ligand [Ltot] allowed calculation of K_(Ca) at various [Ca tot]/[L tot] ratios. Athird titration, adding Ca ion to a solution of a fixed [L tot] andfixed [Mg tot] was compared with K_(Ca) at different [Ca tot]/[L tot]ratios to reveal K_(Mg) at those same ratios. ##EQU1##

At high ratios of [Ca tot]/[L tot], the ligand became saturated with Caion and a linear increase in [Ca free] resulted. This line wasextrapolated back to [Ca free]=0 and [Ca tot] at that point representeda measure of calcium binding capacity.

pH was always 9.55, temperature 22° C. Ionic strength ca. 0.1M, [Catot]=0 to 1.4 mM (0 to 8.2 gr/gal), [Ligand total]=3.52×10⁻⁴ M, [Mgtotal]=2.0 mM.

    ______________________________________                                        Calcium Ion Binding Constants                                                 (35° C., 0.1 M ionic strength, pH 9.5)                                                      Log K.sub.Ca                                             ______________________________________                                        Sodium tripolyphosphate                                                                              4.9                                                    Nitrilotriacetic acid, sodium salt                                                                   5.5                                                    2-oxa-1,1,3 propanetricarboxylic acid,                                                               4.3                                                    sodium salt                                                                   2-oxa-1,3,4 butanetricarboxylic acid,                                                                3.7                                                    sodium salt                                                                   3-oxa-1,2,4,5-pentanetetracarboxylic acid                                                            4.7                                                    sodium salt                                                                   Sodium citrate         3.5                                                    ______________________________________                                    

IRON AND MANGANESE CHELATING AGENT

The detergent compositions of the invention contain from about 0.1% toabout 10%, preferably from about 0.5% to about 10%, more preferably fromabout 0.75% to about 6% and most preferably from about 0.75% to about3%, by weight of an iron and manganese chelating agent or mixturesthereof. Preferably the weight ratio of ether polycarboxylate tochelating agent is from about 3:1 to about 40:1, more preferably fromabout 10:1 to about 30:1 and most preferably from about 15:1 to about30:1.

The iron and manganese chelating agents of the invention are selectedfrom the group consisting of amino carboxylates, amino phosphonates,polyfunctionally--substituted aromatic chelating agents and mixturesthereof, all as hereinafter defined.

Without relying on theory, it is speculated that the benefit of thesematerials is due in part to an exceptional ability to remove iron andmanganese ions from washing solutions by formation of soluble chelates.

Amino carboxylates useful in compositions of the invention have one ormore, preferably at least two, units, of the substructure ##STR11##wherein M is hydrogen, alkali metal, ammonium or substituted ammonium(e.g. ethanolamine) and x is from 1 to about 3, preferably 1.Preferably, said amino carboxylates do not contain alkyl or alkenylgroups with more than about 6 carbon atoms. Alkylene groups can beshared by substructures.

Included are ethylenediaminetetraacetates,N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates,ethylenediamine tetrapropionates, diethylenetriaminepentaacetates, andethanoldiglycines.

Amino phosphonates are suitable in the compositions of the inventionwhen at least low levels of total phosphorus are permitted in detergentcompositions. Compounds with one or more, preferably at least two, unitsof the substructure ##STR12## wherein M is hydrogen, alkali metal,ammonium or substituted ammonium and x is from 1 to about 3, preferably1, are useful and includeethylenediaminetetrakis(methylenephosphonates),nitrilotris(methylenephosphonates) anddiethylenetriaminepentakis(methylenephosphonates). Preferably, saidamino phosphonates do not contain alkyl or alkenyl groups with more thanabout 6 carbon atoms. Alkylene groups can be shared by substructures.

Polyfunctionally--substituted aromatic chelating agents of the inventioncomprise compounds having the general formula ##STR13## wherein at leastone R is --SO₃ H or --COOH or soluble salts thereof and mixturesthereof.

U.S. Pat. No. 3,812,044 issued May 21, 1974, to Connor et al,incorporated herein by reference, disclosespolyfunctionally--substituted aromatic chelating and sequesteringagents.

Preferred compounds in acid form are dihydroxydisulfobenzenes and1,2-dihydroxy-3,5-disulfobenzene or other disulfonated catechols inparticular. Alkaline detergent compositions can contain these materialsin the form of alkali metal, ammonium or substituted ammonium (e.g.mono- or triethanolamine) salts.

POLYMERIC POLYCARBOXYLATE DISPERSING AGENT

The detergent compositions of the invention contain from about 0.5% toabout 10%, preferably from about 0.75% to about 6%, and most preferablyfrom about 0.75% to about 3% by weight of one or more polymericpolycarboxylate dispersing agents, copolymers thereof and salts thereofcontaining at least about 60% by weight of segments with the generalformula ##STR14## wherein X, Y, and Z are each selected from the groupconsisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy andhydroxymethyl; M is hydrogen, alkali metal, ammonium or substitutedammonium and n is from about 30 to about 400. Preferably, X is hydrogenor hydroxy, Y is hydrogen or carboxy and Z is hydrogen.

The polymeric polycarboxylates of greatest value in compositions of theinvention are those that provide a dispersant effect for particulatesoil or other insoluble material in the washing solution. Thischacteristic is related to, but not identical with, precipitationmodification as disclosed in U.S. Pat. No. 3,896,056 issued July 22,1975, to Benjamin et al, incorporated herein by reference.

Preferably, the weight ratio of polymeric polycarboxylate dispersingagent to iron and manganese chelating agent is in the range of fromabout 3:1 to about 1:3, most preferably from about 2:1 to about 1:2.Suitable polymeric polycarboxylates generally include those disclosed inU.S. Pat. No. 3,308,067 issued Mar. 7, 1967, to Diehl, incorporatedherein by reference. Unsaturated monomeric acids that can be polymerizedto form suitable polymeric polycarboxylates include acrylic acid, maleicacid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presenceof monomeric segments containing no carboxylate radicals such asvinylmethyl ether, styrene, ethylene, etc. is suitable provided thatsuch segments do not constitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates are polyacrylates withan average molecular weight in acid form of from about 1,000 to about10,000, and acrylate/maleate or acrylate/fumarate copolymers with anaverage molecular weight of from about 2,000 to about 20,000 and a ratioof acrylate to maleate or fumarate segments of from about 30:1 to about2:1. This and other suitable copolymers based on a mixture ofunsaturated mono- and dicarboxylate monomers are disclosed in EuropeanPatent Applicant No. 66,915, published Dec. 15, 1982, incorporatedherein by reference.

Although the polymeric polycarboxylates contribute to the alkaline earthmetal ion sequestration provided by the ether polycarboxylate component,the optimum molecular weight for dispersing of particulate material inthe washing solution is generally lower than the molecular weightoptimum for multivalent metal ion sequestration.

OPTIONAL DETERGENCY BUILDERS

The detergent compositions of the present invention can containdetergency builders in addition to the essential combination describedherein.

Suitable additional polycarboxylate detergency builders include the acidform and alkali metal, ammonium and substituted ammonium salts ofcitric, ascorbic, phytic, mellitic, benzene pentacarboxylic,cyclohexanehexacarboxylic and cyclopentanetetracarboxylic acids.

Non-amino polyphosphonate detergency builders comprise organic compoundshaving two or more ##STR15## groups wherein M is hydrogen, alkali metal,ammonium or substituted ammonium. Suitable phosphonates includeethane-1-hydroxy-1,1-diphosphonates, ethanehydroxy-1,1,2-triphosphonatesand their oligomeric ester chain condensates. In common with otherphosphorus-containing components, the incorporation of phosphonates maybe restricted or prohibited by government regulation.

As discussed hereinbefore C₈₋₂₄ alkyl monocarboxylic acid and solublesalts thereof have a detergent builder function in addition tosurfactant characteristics. C₁₀ -C₂₀ alkyl, alkenyl, alkoxy and alkylthio-substituted dicarboxylic acid compounds, such as4-pentadecene-1,2-dicarboxylic acid, salts thereof and mixtures thereof,are also useful optional detergency builders.

Inorganic detergency builders useful in the compositions of theinvention at total combined levels of from 0% to about 75% by weight,include alkali metal phosphates, sodium aluminosilicates, alkali metalsilicates and alkali metal carbonates.

Granular laundry detergent compositions generally contain at least about40% of inorganic salts and it is desirable that a major portion of suchsalts have a contribution to the detergent effect. Inorganic detergencybuilders are less useful in liquid detergent compositions of theinvention and can be omitted to provide optimum physical properties andoptimum levels of the essential components.

Phosphate detergency builders include alkali metal orthophosphates whichremove multivalent metal cations from laundry solutions by precipitationand the polyphosphates such as pyrophosphates, tripolyphosphates andwater-soluble metaphosphates that sequester multivalent metal cations inthe form of soluble complex salts. Sodium pyrophosphate and sodiumtripolyphosphate are particularly suitable in granular detergentcompositions and potassium pyrophosphate is suitable in liquid detergentcompositions to the extent that governmental regulations do not restrictor prohibit the use of phosphorus-containing compounds in detergentcompositions. Granular detergent composition embodiments of theinvention particularly adapted for use in areas where the incorporationof phosphorus-containing compounds is restricted contains low totalphosphorus and, preferably, essentially no phosphorus.

Crystalline aluminosilicate ion exchange materials useful in thepractice of this invention have the formula Na_(z) [(AlO₂)_(z).(SiO₂)y]xH₂ O wherein z and y are at least about 6, the molar ratio of zto y is from about 1.0 to about 0.5 and x is from about 10 to about 264.In a preferred embodiment the aluminosilicate ion exchange material hasthe formula Na₁₂ [(AlO₂)₁₂ (SiO₂)₁₂ ]xH₂ O wherein x is from about 20 toabout 30, especially about 27.

Amorphous hydrated aluminosilicate material useful herein has theempirical formula: Na_(z) (zAlO₂.ySiO₂), z is from about 0.5 to about 2,y is 1 and said material has a magnesium ion exchange capacity of atleast about 50 milligram equivalents of CaCO₃ hardness per gram ofanhydrous aluminosilicate.

The aluminosilicate ion exchange builder materials herein are inhydrated form and contain from about 10% to about 28% of water by weightif crystalline and potentially even higher amounts of water ifamorphous. Highly preferred crystalline aluminosilicate ion exchangematerials contain from about 18% to about 22% water in their crystalmatrix. The crystalline aluminosilicate ion exchange materials arefurther characterized by a particle size diameter of from about 0.1micron to about 10 microns. Amorphous materials are often smaller, e.g.,down to less than about 0.01 micron. Preferred ion exchange materialshave a particle size diameter of from about 0.2 micron to about 4microns. The term "particle size diameter" herein represents the averageparticle size diameter of a given ion exchange material as determined byconventional analytical techniques such as, for example, microscopicdetermination utilizing a scanning electron microscope. The crystallinealuminosilicate ion exchange materials herein are usually furthercharacterized by their calcium ion exchange capacity, which is at leastabout 200 mg. equivalent of CaCo₃ water hardness/gm. of aluminosilicate,calculated on an anhydrous basis, and which generally is in the range offrom about 300 mg.eq./g. to about 352 mg. eq./g. The aluminosilicate ionexchange materials herein are still further characterized by theircalcium ion exchange rate which is at least about 2 grainsCa.++/gallon/minute/gram of aluminosilicate (anhydrous basis), andgenerally lies within the range of from about 2grains/gallons/minute/gram to about 6 grains/gallons/minute/gram, basedon calcium ion hardness. Optimum aluminosilicate for builder purposesexhibit a calcium ion exchange rate of at least about 4grains/gallons/minute/gram.

The amorphous aluminosilicate ion exchange materials usually have a Mg++exchange capacity of at least about 50 mg. eq. CaCO₃ /g (12 mg. Mg++/g.)and a Mg++ exchange rate of at least about 1 gr./gal./min./g./gal.Amorphous materials do not exhibit an observable diffraction patternwhen examined by Cu radiation (1.54 Angstrom Units).

Aluminosilicate ion exchange materials useful in the practice of thisinvention are commercially available. The aluminosilicates useful inthis invention can be crystalline or amorphous in structure and can benaturally-occurring aluminosilicates or synthetically derived. A methodfor producing aluminosilicate ion exchange materials is discussed inU.S. Pat. No. 3,985,669, issued Oct. 12, 1976, incorporated herein byreference. Preferred synthetic crystalline aluminosilicate ion exchangematerials useful herein are available under the designation Zeolite A,Zeolite B, and Zeolite X.

Suitable alkali metal silicates have a mole ratio of SiO₂ : alkali metaloxide in the range of from about 1:1 to about 4:1. The alkali metalsilicate suitable herein include commercial preparations of thecombination of silicon dioxide and alkali metal oxide or carbonate fusedtogether in varying proportions according to, for example, the followingreaction: ##STR16##

The value of m, designating the molar ratio of SiO₂ :Na₂ O, ranges fromabout 0.5 to about 4 depending on the proposed use of the sodiumsilicate. The term "alkali metal silicate" as used herein refers tosilicate solids with any ratio of SiO₂ to alkali metal oxide. Silicatesolids normally possess a high alkalinity content; in addition water ofhydration is frequently present as, for example, in metasilicates whichcan exist having 5, 6, or 9 molecules of water. Sodium silicate solidswith a SiO₂ :Na₂ O mole ratio of from about 1.5 to about 3.5, arepreferred in granular laundry detergent compositions.

Silicate solids are frequently added to granular detergent compositionsas corrosion inhibitors to provide protection to the metal parts of thewashing machine in which the detergent composition is utilized.Silicates have also been used to provide a degree of crispness andpourability to detergent granules which is very desirable to avoidlumping and caking.

Alkali metal carbonates are useful in the granular compositions of theinvention as a source of washing solution alkalinity and because of theability of the carbonate ion to remove calcium and magnesium ions fromwashing solutions by precipitation.

Preferred granular compositions free of inorganic phosphates containfrom about 10% to about 40% by weight sodium carbonate, from 0% to about30% sodium aluminosilicate, from about 0.5% to about 10% sodium silicatesolids, from about 10% to about 35% of the ether carboxylates of theinvention and from about 10% to about 25% surfactant.

Preferred liquid compositions free of inorganic phosphates contain fromabout 8% to about 20% by weight of non-soap anionic surfactants, fromabout 2% to about 18% ethoxylated nonionic surfactants, from about 5% toabout 20% of a C₁₀₋₂₂ alkyl or alkenyl mono-or dicarboxylic acid or saltthereof and from about 5% to about 15% of the ether carboxylates of theinvention.

ADDITIONAL OPTIONAL COMPONENTS

Granular compositions of this invention can contain materials such assulfates, borates, perborates and water of hydration.

Liquid compositions of this invention can contain water and othersolvents. Low molecular weight primary or secondary alcohol exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilizing the surfactant but polyolscontaining from 2 to about 6 carbon atoms and from 2 to about 6 hydroxygroups can be used and can provide improved enzyme stability. Examplesof polyols include propylene glycol, ethylene glycol, glycerine and1,2-propanediol. Ethanol is a particularly preferred alcohol.

The compositions of the invention can contain such materials asproteolytic and amylolytic enzymes, fabric whiteners and brighteners,sudsing control agents, hydrotropes such as sodium toluene or xylenesulfonate, perfumes, colorants, opacifiers, anti-redeposition agents andalkalinity control or buffering agents such as monoethanolamine andtriethanolamine. The use of these materials is known in the detergentart.

Materials that provide clay soil removal/anti-redeposition benefits canalso be incorporated in the detergent compositions of the invention andare particularly useful in liquid compositions of the invention.

These clay soil removal/anti-redeposition agents are usually included atlevels of from about 0.1% to about 10% by weight of the composition.

One group of preferred clay soil removal/anti-redeposition agents arethe ethoxylated amines disclosed in European Patent Application No.112,593 of James M. Vander Meer, published July 4, 1984, incorporatedherein by reference. Another group of preferred clay soilremoval/anti-redeposition agents are the cationic compounds disclosed inEuropean patent application No. 111,965 to Young S. Oh and Eugene P.Gosselink, published June 27, 1984, incorporated herein by reference.Other clay soil removal/anti-redeposition agents which can be usedinclude the ethoxylated amine polymers disclosed in European patentapplication No. 111,984 to Eugene P. Gosselink, published June 27, 1984;the zwitterionic compounds disclosed in European patent application No.111,976 to Donn N. Rubingh and Eugene P. Gosselink, published June 27,1984; the zwitterionic polymers disclosed in European patent applicationNo. 112,592 to Eugene P. Gosselink, published July 4, 1984; and theamine oxides disclosed in U.S. application Ser. No. 516,612 to Daniel S.Connor, filed July 22, 1983, all of which are incorporated herein byreference. Polyethylene glycol can also be incorporated to prvideanti-redeposition and other benefits.

Soil release agents, such as disclosed in the art to reduce oilystaining of polyester fabrics, are also useful in the compositions ofthe invention. U.S. Pat. No. 3,962,152 issued June 8, 1976, to Nicol etal., incorporated herein by reference, discloses copolymers of ethyleneterephthalate and polyethylene oxide terephthalate as soil releaseagents. U.S. Pat. No. 4,174,305 issued Nov. 13, 1979, to Burns et al.,incorporated herein by reference, discloses cellulose ether soil releaseagents.

The detergent compositions of the invention can also include a bleachsystem comprising an inorganic or organic peroxy bleaching agent and, inpreferred compositions, an organic peroxy acid bleach precursor.

Suitable inorganic peroxygen bleaches include sodium perborate mono- andtetrahydrate, sodium percarbonate, sodium persilicate and urea-hydrogenperoxide addition products and the clathrate 4Na₂ SO₄ :2H₂ O₂ :1NaCl.Suitable organic bleaches include peroxylauric acid, peroxyoctanoicacid, peroxynonanoic acid, peroxydecanoic acid, diperoxydodecandioicacid, diperoxyazelaic acid, mono- and diperoxyphthalic acid and mono-and diperoxyisophthalic acid. The bleaching agent is generally presentin the compositions of the invention at a level of from about 5% toabout 35% preferably from about 10% to about 25% by weight.

The compositions of the invention preferably also contain an organicperoxy acid bleach precursor at a level of from about 0.5% to about 10%,preferably from about 1% to about 6% by weight. Suitable bleachprecursors are disclosed in No. UK-A-2040983, and include for example,the peracetic acid bleach precursors such as tetraacetylethylenediamine,tetraacetylmethylenediamine, tetraacetylhexylenediamine, sodiump-acetoxybenzene sulfonate, tetraacetylglycouril, pentaacetylglucose,octaacetyllactose, and methyl o-acetoxy benzoate. Highly preferredbleach precursors, however, have the general formula ##STR17## wherein Ris an alkyl group containg from 6 to 12 carbon atoms wherein the longestlinear alkyl chain extending from and including the carboxyl carboncontains from 5 to 10 carbon atoms and L is a leaving group, theconjugate acid of which has a logarithmic acidity constant in the rangefrom 6 to 13.

The alkyl group, R, can be either linear or branched and, in preferredembodiments, it contains from 7 to 9 carbon atoms. Preferred leavinggroups L have a logarithmic acidity constant in the range from about 7to about 11, more preferably from about 8 to about 10. Examples ofleaving groups are those having the formula ##STR18## wherein Z is H, R¹or halogen, R¹ is an alkyl group having from 1 to 4 carbon atoms, X is 0or an integer of from 1 to 4 and Y is selected from SO₃ M, OSO₃ M, CO₂M, N⁺ (R¹)₃ O⁻ and N⁺ (R¹)₂ --O⁻ wherein M is H, alkali metal, alkalineearth metal, ammonium or substituted ammonium, and O is halide ormethosulfate.

The preferred leaving group L has the formula (a) in which Z is H, x is0 and Y is sulfonate, carboxylate or dimethylamine oxide radical. Highlypreferred materials are sodium 3,5,5,-trimethylhexanoyloxybenzenesulfonate, sodium 3,5,5-trimethylhexanoyloxybenzoate, sodium2-ethylhexanoyl oxybenzenesulfonate, sodium nonanoyl oxybenzenesulfonate and sodium octanoyl oxybenzenesulfonate, the acyloxy group ineach instance preferably being p-substituted.

The bleach activator herein will normally be added in the form ofparticles comprising finely-divided bleach activator and a binder. Thebinder is generally selected from nonionic surfactants such as theethoxylated tallow alcohols, polyethylene glycols, anionic surfactants,film forming polymers, fatty acids and mixtures thereof. Highlypreferred are nonionic surfactant binders, the bleach activator beingadmixed with the binder and extruded in the form of elongated particlesthrough a radial extruder as described in European Patent ApplicationNo. 62523. Alternatively, the bleach activator particles can be preparedby spray drying.

EXAMPLES

The following embodiments illustrate, but are not limiting of, detergentcompositions of the present invention. All percentages herein are byweight unless indicated otherwise.

EXAMPLE I

A granular detergent composition for household laundry use is asfollows:

    ______________________________________                                        Component                    Wt. %                                            ______________________________________                                        Sodium C.sub.14 -C.sub.15 alkylsulfate                                                                         13.3                                         Sodium C.sub.13 linear alkyl benzene sulfonate                                                                 5.7                                          C.sub.12 -C.sub.13 alkylpolyethoxylate (2.5)                                                                   1.0                                          Sodium toluene sulfonate         1.0                                          3-oxa-1,2,4,5-pentanetetracarboxylic acid,                                                                     25.0                                         sodium salt                                                                   Sodium N--hydroxyethyethylenediamine-                                                                          2.0                                          triacetate                                                                    Sodium polyacrylate (Avg. M.W. = ±5000)                                                                     2.0                                          Sodium carbonate                 20.3                                         Sodium silicate                  5.8                                          Polyethylene glycol (Avg. M.W. ±8000)                                                                       1.0                                          Sodium sulfate, water and miscellaneous                                                              Balance to                                                                              100                                          ______________________________________                                    

In the composition of Example I the following substitutions are made:

(a) for 3-oxa 1,2,4,5-pentanetetracarboxylic acid, sodium salt

(1) 2-oxa-1,1,3-propanetricarboxylic acid, sodium salt

(2) 2-oxa-1,3,4-butanetricarboxylic acid, sodium salt

(3) a polyacetal carboxylate with the approximate formula ##STR19## (b)for N-hydroxyethylethylenediaminetriacetate, sodium salt (1)diethylenetriaminepentakis(methylenephosphonate), sodium salt

(2) 1,2-dihydroxy-3,5-disulfobenzene, sodium salt

(c) for sodium polyacrylate (avg. M.W.=±5000)

(1) sodium salt of an acrylate/maleate copolymer (avg. M.W.=9000) inwhich the acrylate/maleate weight ratio is approximately 7:3.

The components are added together with continuous mixing with sufficientextra water (about 40% total) to form an aqueous slurry which is thenspray dried to form the composition.

EXAMPLE II

A liquid detergent composition for household laundry use is as follows:

    ______________________________________                                        Component                    Wt. %                                            ______________________________________                                        Potassium C.sub.14 -C.sub.15 alkyl polyethoxy                                                                  8.3                                          (2.5) sulfate                                                                 C.sub.12 -C.sub.14 alkyl dimethyl amine oxide                                                                  3.3                                          Potassium toluene sulfonate      5.0                                          Monoethanolamine                 2.3                                          2-oxa-1,1,3-propanetricarboxylic acid,                                                                         15.0                                         potassium salt                                                                Sodium salt of 1,2-dihydroxy-    1.5                                          3,5-disulfobenzene                                                            Sodium polyacrylate (avg. M.W. = ±9000)                                                                     1.5                                          Minors and water       Balance to                                                                              100                                          ______________________________________                                    

The components are added together with continuous mixing to form thecomposition.

EXAMPLE III

A liquid detergent composition for household laundry use is prepared bymixing the following ingredients:

    ______________________________________                                        C.sub.13 alkylbenzenesulfonic acid                                                                             10.5%                                        Triethanolamine cocoalkyl sulfate                                                                              4.0                                          C.sub.14-15 alcohol ethoxy-7     12.0                                         C.sub.12-18 alkyl monocarboxylic acids                                                                         15.0                                         3-oxa-1,2,4,5-pentanetetracarboxylic acid                                                                      5.0                                          Diethylenetriaminepentamethylene 0.8                                          phosphonic acid                                                               Polyacrylic acid (avg. M.W. = ±5000)                                                                        0.8                                          Triethanolamine                  4.5                                          Ethanol                          8.6                                          1,2-Propanediol                  3.0                                          Water, perfume, buffers and miscellaneous                                                            Balance to                                                                              100                                          ______________________________________                                    

3,3-dicarboxy-4-oxa-1,6-hexanedioic acid is substituted for3-oxa-1,2,4,5-pentanetetracarboxylic acid.

The acrylate/maleate copolymer of Example I in acid form is substitutedfor polyacrylic acid.

N-hydroxyethylethylenediaminetriacetic acid is substituted fordiethylenetriaminepentakis(methylenephosphonic) acid.

EXAMPLE IV

In the Compositions which follow, the abbreviations used have thefollowing designations:

C₁₂ LAS: Sodium linear C₁₂ benzene sulfonate

TAS: Sodium tallow alcohol sulfonate

TAE_(n) : Hardened tallow alcohol ethoxylated with n moles of ethyleneoxide per mole of alcohol

Dobanol 45_(E) 7: A C₁₄₋₁₅ primary alcohol condensed with 7 moles ofethylene oxide

TAED: Tetraacetyl ethylene diamine

NOBS: Sodium nonanoyl oxybenzenesulfonate

INOBS: Sodium 3,5,5 trimethyl hexanoyl oxybenzene sulfonate

Silicate: Sodium silicate having an SiO₂ :Na₂ O ratio of 1:6

Sulfate: Anhydrous sodium sulfate

Carbonate: Anhydrous sodium carbonate

CMC: Sodium carboxymethyl cellulose

Silicone: Comprising 0.14 parts by weight of an 85:15 by weight mixtureof silanated silica and silicone, granulated with 1.3 parts of sodiumtripolyphosphate, and 0.56 parts of tallow alcohol condensed with 25molar proportions of ethylene oxide

PC1: Copolymer of 3:7 maleic/acrylic acid, average molecular weightabout 70,000, as sodium salt

PC2: Polyacrylic acid, average molecular weight about 4,500, as sodiumsalt

PESA: Polyepoxysuccinic acid of formula HO--[CH(COOH)--CH(COOH)--O]_(n)--H n averaging about 10 (contains at least about 25% by weight wheren=2-4), M.W. (as Na salt, by NMR)=950, Log K_(Ca) =5.3

Perborate: Sodium perborate tetrahydrate of nominal formula NaBO₂.3H₂O.H₂ O₂

Enzyme: Protease

EDTA: Sodium ethylene diamine tetra acetate

Brightener: Disodium4,4'-bis(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'disulfonate

DETPMP: Diethylene triamine penta(methylene phosphonic acid), marketedby Monsanto under the Trade name Dequest 2060

EDTMP: Ethylenediamine tetra(methylene phosphonic acid), marketed byMonsanto, under the Trade name Dequest 2041

Granular detergent compositions are prepared as follows. A base powdercomposition is first prepared by mixing all components except, wherepresent, Dobanol 45E7, bleach, bleach activator, enzyme, sudssuppressor, phosphate and carbonate in crutcher as an aqueous slurry ata temperature of about 55° C. and containing about 35% water. The slurryis then spray dried at a gas inlet temperature of about 330° C. to formbase powder granules. The bleach activator, where present, is thenadmixed with TAE₂₅ as binder and extruded in the form of elongatedparticles through a radical extruder as described in European PatentApplication No. 62523. The bleach activator noodles, bleach, enzyme,suds suppressor, phosphate and carbonate are then dry-mixed with thebase powder composition and finally Dobanol 45E7 is sprayed into thefinal mixture.

    ______________________________________                                        COMPOSITIONS                                                                                 A    B        C      D                                         ______________________________________                                        C.sub.12 LAS     4      9        8    8                                       TAS              4      3        --   3                                       TAE.sub.25       0.5    0.5      0.8  --                                      TAE.sub.11       --     1        --   --                                      Dobanol 45E7     4      --       4    2                                       NOBS             --     2        --   --                                      INOBS            3      --       --   --                                      TAED             0.5    --       3    --                                      Perborate        19     20       10   24                                      EDTMP            0.3    --       0.4  0.1                                     DETPMP           --     0.4      --   --                                      EDTA             0.2    0.2      0.2  0.1                                     Magnesium (ppm)  1000   1000     750  --                                      PC1              2      1        2    2                                       PC2              1      1        --   1                                       PESA             25     7        15   10                                      Zeolite A*       --     15       14   --                                      Sodium tripolyphosphate                                                                        --     --       --   12                                      Coconut Soap     --     --       --   2                                       Carbonate        17     15       10   --                                      Silicate         3      2        2    7                                       Silicone         0.2    0.2      0.3  0.2                                     Enzyme           0.8    0.5      0.4  0.3                                     Brightener       0.2    0.2      0.2  0.2                                     Sulfate,         to 100                                                       Moisture &                                                                    Miscellaneous                                                                 ______________________________________                                         *Zeolite A of 4 A pore size.                                             

The above compositions are zero and low phosphate detergent compositionsdisplaying excellent bleach stability, fabric care and detergencyperformance across the range of wash temperatures with particularlyoutstanding performance in the case of Compositions A, B and C on greasyand particulate soils at low wash temperatures.

What is claimed is:
 1. A detergent composition comprising:(a) from about2% to about 30% by weight of a surfactant selected from the groupconsisting of anionic, nonionic, zwitterionic, ampholytic and cationicsurfactants and mixtures thereof; (b) from about 15% to about 40% of anether polycarboxylate compound or mixtures thereof of the structure:##STR20## wherein R₁ and R₂ are each independently H, COOM or CH₂ COOMand wherein R₁ and R₂ are not both H and wherein M is hydrogen, analkali metal, ammonium or substituted ammonium and said compound has alog K_(Ca) (35° C., 0.1M ionic strength, pH 9.5) of at least about 3.6;(c) from about 0.75% to about 3% by weight of an iron and manganesechelating agent selected from the group consisting of: 1) aminocarboxylates having one or more units of the substructure: ##STR21##wherein M is hydrogen, an alkali metal, ammonium or substitutedammonium, and x is from 1 to about 3, (2) amino phosphonates having oneor more units of the substructure: ##STR22## wherein M is hydrogen, analkali metal, ammonium or substituted ammonium and x is from 1 to about3, 3) polyfunctionally-substituted aromatic chelating agents consistingof compounds having the formula: ##STR23## wherein at least one R is--SO₃ H, or --COOH or soluble salts thereof and mixtures thereof and 4)mixtures thereof; (d) from about 0.75% to about 3% by weight of one ormore polymeric polycarboxylic acid dispersing agents, copolymers thereofand salts thereof containing at least about 60% by weight of segmentswith the general formula: ##STR24## wherein X, Y and Z are each selectedfrom the group consisting of hydrogen, methyl, and carboxy; M ishydrogen, alkali metal, ammonium or substituted ammonium and n is fromabout 30 to about 400; and (e) from 0% to about 75% by weight of aninorganic detergency builder selected from the group consisting ofalkali metal phosphates, sodium carbonate, sodium silicate, sodiumaluminosilicate and mixtures thereof.
 2. The composition of claim 1wherein the ether polycarboxylate has a log K_(Ca) of at least about4.2.
 3. The composition of claim 1 wherein the ether polycarboxylatecomprises a material selected from the group consisting of 2-oxa-1,1,3propanetricarboxylic acid, 2-oxa-1,3,4 butanetricarboxylic acid,3-oxa-1,2,4,5-pentanetetracarboxylic acid, mixtures thereof and alkalimetal, ammonium and substituted ammonium salts thereof.
 4. Thecomposition of claim 1 wherein the iron and manganese chelating agentcomprises a material selected from the group consisting ofethylenediaminetetraacetates, diethylenetriaminepentaacetates,N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates,ethanoldiglycines, ethylenediaminetetrakis(methylenephosphonates),nitrilotris(methylenephosphonates),diethylenetriaminepentakis(methylenephosphonates), disulfonatedcatechols, mixtures thereof and alkali metal, ammonium and substitutedammonium salts thereof.
 5. The composition of claim 3 wherein thepolymeric polycarboxylate comprises a material selected from the groupconsisting of polyacrylates, copolymers of acrylates and maleates,mixtures thereof and alkali metal, ammonium and substituted ammoniumsalts thereof.
 6. The composition of claim 1 wherein said composition isa granular detergent composition comprising from about 15% to about 60%of an inorganic detergency builder selected from the group consisting ofsodium carbonate, sodium silicate and mixtures thereof and from about15% to about 40% of sodium salts of said ether polycarboxylate compoundor mixtures thereof.
 7. The composition of claim 5 wherein saidsurfactant comprises an anionic surfactant selected from the groupconsisting of alkyl sulfates, alkyl ether sulfates, alkylbenzenesulfonates and mixtures thereof.
 8. The composition of claim 6 whereinsaid ether polycarboxylate comprises a material selected from the groupconsisting of the sodium salts of 2-oxa-1,1,3-propanetricarboxylic acid,2-oxa-1,3,4-butanetricarboxylic acid,3-oxa-1,2,4,5-pentanetetracarboxylic acid, and mixtures thereof.
 9. Thecomposition of claim 7 containing essentially no phosphorus.
 10. Thecomposition of claim 8 which comprises an alkali metal salt of apolymeric polycarboxylate selected from the group consisting ofpolyacrylates, copolymers of acrylates and maleates and mixturesthereof.
 11. The composition of claim 1 wherein said composition is aliquid detergent composition comprising from about 5% to about 15% ofsaid ether polycarboxylate or mixture thereof.
 12. A compositionaccording to claim 1 additionally comprising from about 5% to about 35%by weight of inorganic or organic peroxy bleaching agent.
 13. Acomposition according to claim 11 additionally comprising from about0.5% to about 10% by weight of organic peroxyacid bleach precursor. 14.A composition according to claim 12 wherein the bleach precursor has thegeneral formula: ##STR25## wherein R is an alkyl group containing from 6to 12 carbon atoms wherein the longest linear alkyl chain extending fromand including the carboxyl carbon contains from 5 to 10 carbon atoms andL is a leaving group, the conjugate acid of which has a logarithmicacidity constant in the range from 6 to 13.